We have observed the diatomic $nsns\ensuremath{\rightarrow}ns(n+1)s\ensuremath{\rightarrow}(n+1)s(n+1)s$ microwave transitions of pairs of cold Rb Rydberg atoms for
36<n<48. The
ns(n+1)s state has by far the largest van der Waals shift due to its near degeneracy with the nearby
np3/2np3/2 state. In fact, the energy difference and the van der Waals shift change sign at
n=38 and we observe shifts of both signs. The combined excitation of the
ns(n+1)s and
(n+1)s(n+1)s states leads to an unusual line shape which can be described by a three-level Floquet model.